Synthetic oil



TN FFICE sm'rns'rlo on.

Charles C. Towne, Beacon, N. Y., assignor to The Texas Company, New York, N. Y., a corporation of Delaware No Drawing. Original application August 3, 1934,

Serial No. 738,293. Divided and this application August 27, 1936, Serial No. 98,235

3 Claims.

The present invention relates to the preparation of resinous and oily condensation products from benzene and halides of normally gaseous olefines;.

This is a division of my co-pending application invention contemplates the manufacture of synthetic resins or oils from benzene and a halide of a normally gaseous olefine, such as ethylene or propylene chloride. I am aware that the literature discloses the preparation of lower boiling condensation products, such as dibenzyl, by the Friedel-Craft reaction, by condensing benzene with hydrocarbon halides in the presence of aluminum chloride. I have discovered that by control of the proportions of the reactants and the conditions of the reaction, substantial yields of synthetic resins or viscous oils can be produced.

In accordance with the present invention, benzene is mixed with a halide of a normally gaseous olefine, such as ethylene or propylene chloride, at normal or atmospheric temperatures and pressures; and a quantity of a condensation catalyst, either of the Friedel Craft type such as aluminum chloride, or metallic aluminum, is added. The mixture is stirred and may be gently heated to start reaction, although this usually is unnecessary. During the reaction, considerable heat may be generated, and the temperature is preferably controlled by a cooling bath to prevent a rise above about 60 C. In order to produce a resin, proportions of the order of 1-2 parts of benzene, 8 parts'of theolefine halide, and 1 part of alumi num chloride, by weight, give very satisfactory results. On the other hand, where a viscous oil of the character of a lubricating or transformer oil is desired, proportions of the order of 10-12 parts of benzene to 8 parts of the olefine halide with 1 part of aluminum chloride, by weight, are satisfactory. Intermediate amounts of benzene between the proportions specified above give viscous oily condensation products whichhavethe characteristics of synthetic drying oils.

In the case of the production of a resin from ethylene chloride and benzene, a -Friedel-Craft catalyst of the character of aluminum chloride is preferred. On the other hand, propylene chloride reacts efiectively with benzene in the presence of either metallic aluminum or a Friedel-Craft cata- Serial No. 738,293, filed August 3, 1934 now U. S.

lyst. Care should also be exercised in the production of a resin from ethylenechloride and benzene with the proportions of ingredients specified above, because if the reaction is allowed to continue much in excess of about 15 to 20 minutes, a sudden gel formation may occur, which does not decompose even when boiled with. the addition of water. However, when the reaction is terminated prior to the gel stage, such as by the addition of water or an alkaline solution which effects the decomposition of the aluminum addition compounds, a very satisfactory resin is obtained. While a comparatively short reaction time is sufficient for the production of resins with the proportions stated, a longer reaction time of the order of Ito 3 hours or more is preferably provided in the case of the production of viscous oils, where higher proportions of benzene are employed. In either case, water or an alkaline solution may be added to the total reaction material to cause decomposition and solution ofthe catalyst, which may then be removed as a lower aqueous layer, preferably after the addition of a solvent for the condensation product, such as benzol. Resin is recovered from the dried upper oily layer by distilling off the solvent and lower boiling polymers. In the case of production of oily condensation products, the same procedure may be employed or the reaction material may first be allowed to stand, whereupon it stratifies into an upper oily layer containing substantially all of the benzene and lower boiling oily polymers,

Y and a lower sludge layer which is made up of viscous oil in chemical combination with the catalyst. These may be separated by decantation, whereupon viscous oils of varying properties may be obtained.

' The following are listed as specific examples of the present invention:

Example 1 To a mixture of 400 g. of ethylene chloride, C2H4C12, and 50 g. of benzene, 50 g. of aluminum chloride were added. With agitation, the temperature rose from 22 C. to 48 C. After a reaction time of 12 minutes, 500 cc. of hot water were added to decompose the reaction product and dissolve the catalyst, which was separated as a lower aqueous layer following the addition of benzol to insure solution of resinous condensation cast. By. heating at 175-200 0., the resin came very hard.

Example 2 200 g. of propylene chloride, CaHsClz, were mixed with g. of'benzene and 25 g. of aluminum chloride, the reaction temperature rising from 25 C. to 52 C. After a reaction time of 1 hour, the product was decomposed by the addition of water, and the catalyst removed as a lower aqueous layer, following the addition of benzol. After vaporization of solvent and lower boiling liquids from the benzol layer, 44 g. of a solid hard brittle orange-red resin were obtained.

, Example 3 1000 g. of ethylene chloride, 1580 g. of benzene and 125 g. of aluminum chloride were mixed and warmed to 36 (2., when reaction set in and continued without further application of heat until a reaction temperature of 45 C. was reached. The reaction products were then further heated to 60 C. when further reaction set in. The material was then allowed to stand for about 12 hours, when it stratified into a top oil layer and a bottom sludge layer. The top oil layer was washed with Water and alkali and distilled to remove a cut boiling between 250-300 C. containing dibenzyl and amounting to 221 g., leaving an oily residue of golden color amounting to 344 g. The bottom sludge layer contained a green oil amounting to 310 g. Tests on the golden oil and the green oil yielded the following properties:

Golden oil Green oil Specific gravity 1. 031 l. 041 Flash, F 340 240 Fire, F 390 335 Viscosity at 100 F- 174 403 Viscosity at 210 F 44 60 Viscosity indexour, F -25 +20 Carbon residue, percent. 2. 99 7. 9 Iodine number l. 0 7. 0 Sligh number 4. 7 799 Percent 01 None 025 Eicample 4 1130 g. of propylene chloride were mixed with 1560 g. of benzene and g. of aluminum chloride. The aluminum chloride was added slowly in small proportions during hour. The reaction started slowly but then proceeded rapidly,

Top oil Sludge oil 8 cific gravity Fifish, F Fire, F Viscosity at 100 F 480 Viscosity at F 1770 Viscosity at 210 F 52 124 Viscosity index- 9 Less than 0 Pour, I 0 2. 7 7 6. 0 70 1. 2 133 None It is to be noted that the lower viscosity 'upon exposure, and when a mixture consisting essentially of such as aniline and nitromethane, at room temperature, which distinguishes them from petroleum lubricating oils which are ingeneral immiscible with such solvents at ordinary temperatures.

Where intermediate proportions of benzene are employed, such forexample as about 2-10 parts by weight of benzene to 8 parts by weight of ethylene or propylene chloride, in the presence of about 1-2 parts by weight of a condensation catalyst of the character specified above, viscous sticky oils are produced which have the general properties of drying oils. Thus, these oils oxidize painted on panels dry to a tough hard film.

Other halide addition products of the oleflnes may be used, such as the bromides. In place of metallic aluminum or aluminum chloride, other condensation catalysts of .the Friedel-Craft type can be employed, such as the halides of iron, boron, nickel, tin, zinc,'-ahtimony, cadmium and manganese.

Obviously many modifications and variations of the invention, as hereinbefore set forth, may

be made without departing from the spirit and scope thereof, "and therefore only such limitations should be imposed as are indicated in the appended claims.

I claim:

1. The method in the manufacture of a synthetic lubricating oil which comprises condensing about eight parts by weight of an olefin dichloride selected from the group consisting ofethylene chloride and propylene chloride and about 10-12 parts by weight of benzene in the presence of about 1-2 parts by weight metallic halide catalyst at temperatures below about 60" C., the proportions of the reactants and the time of reaction being controlled to prevent gelling and to give a non-gelled liquid condensation product, allowing the con-. densation product to stratify in the absence of added water into an upper oily layer and a lower non-aqueous metallic halide sludge-layer, separating the layers, distilling the separated upper oily layer to remove materials boiling below about 300 C. at atmospheric pressure to obtain as a residue an oily liquid within the lighter lubricating oil range having a specific gravity greater than 1.0, a pour point of the order of 0 F. or below, a comparatively low carbon residue and a high resistance to oxidation as measured by the Sligh number such as to render the oil suitable for use as a transformer oil, both- 'the carbon residue and the Sligh number beiiifis substantially less than would be obtained in tnabsence of stratiflcation and separation of the non' aqueous metallic halide sludge layer from the oily Iayr as above specified.

2. The method in the manufacture of a synthetic lubricating oil which comprises condensing a mixture consisting essentially of about eight parts by weight of ethylene chloride with about 10-12 parts by weight of benzene in the presence of about 1-2 parts by weight of aluminum chloride at temperatures below about 60 C., the proportion of the reactants and the time of reaction being controlled to prevent gelling and to give a non-gelled liquid condensation product, allowing the condensation product to stratify in the absence of added water into an upper oily layer and a lower non-aqueous aluminum chloride sludge layer, separating the layers, distilling the upper oily layer to separate materials including dibenzyl boiling below about 300 C. at atmospheric pressure to obtain a residue of oily liquid of golden color within the lighter lubricating oil range having a specific gravity greater than 1.0, a pour point below 0 F., a high viscosity index, and a comparatively low carbon residue and a high resistance to oxidation as measured by the Sligh number the carbon residue and the Sligh number both being substantially lower than would be obtained in the absence of stratification and separation of the non-aqueous aluminum chloride sludge layer from the oily layer as specified above.

3. The method in the manufacture of a synthetic lubricating oil which comprises condensing a mixture consisting essentially oi about eight parts by weight of propylene chloride and about 10-12 parts by weight of benzene in the presence of about 1-2 parts by weight aluminum chloride at temperatures below about 60 C. to produce a non-gelled liquid condensation product, allowing the condensation product to stratify in the absence of added water into an upper oily layer and a lower non-aqueous aluminum chloride sludge layer, separating the layers, distilling'the separated upper oily layer ing below about 300 C. at atmospheric pressure to obtain as a residue an oily liquid within the lighter lubricating oil range having a specific gravity greater than 1.0, a pour point of the order of 0 F., and a comparatively low carbon residue and a high resistance to oxidation as measured by the Sligh number, the carbon residue and Sligh number both being substantially lower than would be obtained in the absence of stratification and separation of the non-aqueous aluminum chloride sludge layer from the oily layer as specified above.

CHARLES C. TOWNE.

to remove materials boil- 

